EP3240830B1 - Crash-resistente epoxidhaftmittelzusammensetzungen mit verbesserter kälteschlagzähigkeit und abwaschbeständigkeit - Google Patents
Crash-resistente epoxidhaftmittelzusammensetzungen mit verbesserter kälteschlagzähigkeit und abwaschbeständigkeit Download PDFInfo
- Publication number
- EP3240830B1 EP3240830B1 EP15754083.2A EP15754083A EP3240830B1 EP 3240830 B1 EP3240830 B1 EP 3240830B1 EP 15754083 A EP15754083 A EP 15754083A EP 3240830 B1 EP3240830 B1 EP 3240830B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- epoxy
- adhesive
- adhesive composition
- block copolymer
- substrates
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- RREGISFBPQOLTM-UHFFFAOYSA-N alumane;trihydrate Chemical compound O.O.O.[AlH3] RREGISFBPQOLTM-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- UTTHLMXOSUFZCQ-UHFFFAOYSA-N benzene-1,3-dicarbohydrazide Chemical compound NNC(=O)C1=CC=CC(C(=O)NN)=C1 UTTHLMXOSUFZCQ-UHFFFAOYSA-N 0.000 description 1
- IDSLNGDJQFVDPQ-UHFFFAOYSA-N bis(7-oxabicyclo[4.1.0]heptan-4-yl) hexanedioate Chemical compound C1CC2OC2CC1OC(=O)CCCCC(=O)OC1CC2OC2CC1 IDSLNGDJQFVDPQ-UHFFFAOYSA-N 0.000 description 1
- 239000001055 blue pigment Substances 0.000 description 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical class FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 1
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- VDQQXEISLMTGAB-UHFFFAOYSA-N chloramine T Chemical compound [Na+].CC1=CC=C(S(=O)(=O)[N-]Cl)C=C1 VDQQXEISLMTGAB-UHFFFAOYSA-N 0.000 description 1
- 229910001919 chlorite Inorganic materials 0.000 description 1
- 229910052619 chlorite group Inorganic materials 0.000 description 1
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- DGJMPUGMZIKDRO-UHFFFAOYSA-N cyanoacetamide Chemical compound NC(=O)CC#N DGJMPUGMZIKDRO-UHFFFAOYSA-N 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 229920000359 diblock copolymer Polymers 0.000 description 1
- 239000004316 dimethyl dicarbonate Substances 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- XXOYNJXVWVNOOJ-UHFFFAOYSA-N fenuron Chemical compound CN(C)C(=O)NC1=CC=CC=C1 XXOYNJXVWVNOOJ-UHFFFAOYSA-N 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 1
- 239000001056 green pigment Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- INSIURULIZUZHA-UHFFFAOYSA-N oxacyclotridecane Chemical compound C1CCCCCCOCCCCC1 INSIURULIZUZHA-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000013500 performance material Substances 0.000 description 1
- 229960003396 phenacemide Drugs 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003224 poly(trimethylene oxide) Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000001054 red pigment Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000003340 retarding agent Substances 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- DUIOPKIIICUYRZ-UHFFFAOYSA-N semicarbazide Chemical compound NNC(N)=O DUIOPKIIICUYRZ-UHFFFAOYSA-N 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- BPILDHPJSYVNAF-UHFFFAOYSA-M sodium;diiodomethanesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C(I)I BPILDHPJSYVNAF-UHFFFAOYSA-M 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
- 150000003628 tricarboxylic acids Chemical class 0.000 description 1
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
- C09J5/06—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving heating of the applied adhesive
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Definitions
- the present invention relates generally to impact modifiers, and in particular, to thermosetting epoxy resins having improved low-temperature impact resistance, and improved wash-off resistance.
- Epoxy resin based adhesives are used to bond a variety of different substrates together.
- the adhesive must maintain good bonding to the substrate and good impact resistance over a very wide temperature range.
- epoxy resin adhesives are used in the automotive industry in metal-metal bonding in frame and other structures. Adhesive bonding can reduce the number of welds that are needed to construct the frame, and for that reason, the use of these adhesives can reduce assembly costs.
- the adhesive will be subjected to a very wide range of temperatures during subsequent manufacturing processes and during the lifetime of the vehicle. These temperatures may be as high as 80° C. Automobiles that are used in cold climates may be exposed to temperatures as low as -40° C.
- Structural adhesives potentially offer similar advantages in aerospace manufacturing as they do in the automotive sector, such as reduced vehicle weight and reduced manufacturing costs.
- aircraft are routinely exposed to temperatures as low as -60 to -70° C when they operate at altitudes of 30,000 feet or more, which is common in the industry.
- Structural adhesives used in these applications must retain adequate adhesion and impact resistance at these temperatures.
- U.S. Patent Publication No. 2011/0114257 describes an impact modifier containing carboxylic acid group(s), which is prepared from the reaction of an intramolecular anhydride of a di- or tricarboxylic acid with at least one amphiphilic block copolymer containing at least one hydroxyl group.
- the impact modifier is blended with an epoxy resin and is purported to provide improvements in impact resistance at temperatures above or approaching -40° C.
- WO 2005/007720 and U.S. 2007/0066721 an adhesive system is described which contains a polytetrahydrofuran-based toughener based on polytetrahydrofuran (PTHF, also known as polytetramethylene glycol, PTMEG, polytetramethylene oxide, and PTMO).
- PTHF polytetrahydrofuran
- PTMEG polytetrahydrofuran
- PTMO polytetrahydrofuran
- WO 2006/052726 A1 describes a curable adhesive epoxy resin composition including (a) an epoxy resin; (b) an amphiphilic block copolymer containing at least one epoxy resin miscible block segment and at least one epoxy resin immiscible block segment; wherein the immiscible block segment comprises at least one polyether structure provided that the polyether structure of said immiscible block segment contains at least one or more alkylene oxide monomer units having at least four carbon atoms; in an amount such that when the epoxy resin composition is cured, the bond strength of the resulting cured epoxy adhesive resin composition increases compared to an epoxy resin composition without said amphiphilic polyether block copolymer; and (c) at least one curing agent.
- the amphiphilic block copolymer is preferably an all polyether block copolymer such as a PEO-PBO diblock copolymer or a PEO-PBO-PEO triblock copolymer.
- Embodiments of the present invention comprise a one component adhesive composition that may help overcome one or more of the foregoing discussed problems.
- embodiments of the invention provide an epoxy adhesive composition having improved impact resistance at low temperatures, such as -40° C or less.
- a composite structure prepared with the adhesive has an impact peel strength of at least 15 N/mm at a temperature of -40° C, wherein the impact peel strength is measure in accordance with ISO 11343 wedge impact method.
- composite structures prepared with the inventive epoxy adhesive composition may have impact peel strengths of at least 13 N/mm at a temperature of -40° C, wherein the impact peel strength is measure in accordance with ISO 11343 wedge impact method, and preferably at least 15 N/mm, and more preferably, at least 20 N/mm.
- the present invention provides a one component epoxy adhesive composition
- a one component epoxy adhesive composition comprising one or more epoxy resins; at least one polyurethane based toughener; at least one epoxy functionalized amphipathic block copolymer (also known as amphiphilic block copolymer); and one or more epoxy curing agents, wherein the epoxy functionalized amphipathic block copolymer comprises a reaction product of a carboxylic terminated ethylene oxide-butylene oxide block copolymer and an epoxy resin.
- the epoxy resin includes at least one diglycidyl ether of a bisphenol.
- the amount of epoxy may be from about 30 to 60 weight percent, based on the total weight of the epoxy adhesive composition.
- the polyurethane based toughener includes aliphatic diisocyanate groups that are blocked or capped with one or more of Bisphenol A or diisopropyl amine.
- the polyurethane based toughener is a reaction product of an aliphatic diisocyanate and a polyol having a molecular weight ranging between 2,000 and 12,000 Daltons.
- the amount of polyurethane may range from about 10 to 25 weight percent, based on the total weight of the epoxy adhesive composition
- the amount of amphiphilic block copolymer may range from about 2 to 14 weight percent, based on the total weight of the epoxy adhesive composition.
- the epoxy adhesive composition may comprise at least one filler, such as mineral fillers, glass particles, and fused silica.
- the adhesive may also include curing promoting and accelerating agents.
- a further aspect of the invention is also directed to a composite structure comprising a first substrate, a second substrate, and a cured epoxy adhesive composition of the invention that adhesively bonds the first and second substrates together.
- the substrates may be the same material or comprise materials that are different from each other.
- the first and second substrates may both be metal.
- one of the first and second substrates is metal, and the other substrate is plastic.
- aspects of the invention are also directed to methods of joining materials.
- a method comprising applying the inventive epoxy adhesive composition to surfaces of two substrates, and curing the epoxy adhesive composition to form an adhesive bond.
- the one component epoxy adhesive composition may have improved wash off resistance when subjected to an e-bath treatment.
- the epoxy adhesive composition having improved wash off resistance has a viscosity of less than 300 pascal second, more preferably a viscosity from 225 to 300 pascal second, such as from 245 to 280 pascal second, from 250 to 275 pascal second, and from 260 to 270 pascal second.
- the epoxy adhesive composition exhibits an improvement in wash off resistance in comparison to a similar adhesive composition that does not include an epoxy functionalized amphipathic block copolymer. In some embodiments, the epoxy adhesive composition exhibits a wash off resistance of less than 20% as measured as the percent difference between the adhesive composition and an epoxy formulation having a viscosity greater than 350 pascal second when subjected to an indirect impingement spray test.
- embodiments of the present invention exhibit an adhesive wash off resistance of less than 20% when subjected to the e-coat bath treatment, and in particular, less than 18%, and more particularly, less than 15%, and even more particularly, less than 12% as measured as the percent difference between an epoxy formulation having a viscosity greater than 350 pascal second and the inventive formulation when subjected to the indirect impingement spray test.
- embodiments of the present invention are directed to an epoxy based adhesive composition
- an epoxy based adhesive composition comprising one or more epoxy resins; at least one polyurethane based toughener; at least one epoxy functionalized amphipathic block copolymer; and one or more epoxy curing agents, wherein the epoxy functionalized amphipathic block copolymer comprises a reaction product of a carboxylic terminated ethylene oxide-butylene oxide block copolymer and an epoxy resin.
- the epoxy adhesive composition contains at least one epoxy resin. All or part of the epoxy resin may be present in the form of a rubber-modified epoxy resin, as discussed more below.
- a wide range of epoxy resins can be used, including those described at column 2 line 66 to column 4 line 24 of U.S. Pat. No. 4,734,332 .
- Suitable epoxy resins include the diglycidyl ethers of polyhydric phenol compounds such as resorcinol, catechol, hydroquinone, bisphenol, bisphenol A, bisphenol AP (1,1-bis(4-hydroxylphenyl)-1-phenyl ethane), bisphenol F, bisphenol K, bisphenol M, tetramethylbiphenol, diglycidyl ethers of aliphatic glycols and polyether glycols such as the diglycidyl ethers of C 2-24 alkylene glycols and poly(ethylene oxide) or poly(propylene oxide) glycols; polyglycidyl ethers of phenol-formaldehyde novolac resins, alkyl substituted phenol-formaldehyde resins (epoxy novalac resins), phenol-hydroxybenzaldehyde resins, cresol-hydroxybenzaldehyde resins, dicyclopentadiene-phenol resins and dicyclopentadiene-sub
- Suitable diglycidyl ethers include diglycidyl ethers of bisphenol A resins such as are sold by The Dow Chemical Company under the designations D.E.R.® 330, D.E.R.® 331, D.E.R..RTM. 332, D.E.R.® 383, D.E.R.® 661 and D.E.R.® 662 resins.
- diglycidyl ethers of polyglycols include those sold as D.E.R.® 732 and D.E.R.® 736 by The Dow Chemical Company.
- Epoxy novolac resins may also be used. Such resins are available commercially as D.E.N.® 354, D.E.N.® 431, D.E.N.® 438 and D.E.N.® 439 from The Dow Chemical Company.
- a cycloaliphatic epoxide includes a saturated carbon ring having an epoxy oxygen bonded to two vicinal atoms in the carbon ring, as illustrated by the following structure I: wherein R is an aliphatic, cycloaliphatic and/or aromatic group and n is a number from 1 to 10, preferably from 2 to 4. When n is 1, the cycloaliphatic epoxide is a monoepoxide. Di- or epoxy resins are formed when n is 2 or more. Mixtures of mono-, di- and/or epoxy resins can be used. Cycloaliphatic epoxy resins as described in U.S. Pat. No.
- Cycloaliphatic epoxy resins of particular interest are (3,4-epoxycyclohexyl-methyl)-3,4-epoxy-cyclohexane carboxylate, bis-(3,4-epoxy-cyclohexyl) adipate, vinylcyclohexene monoxide and mixtures thereof.
- Suitable epoxy resins may include oxazolidone-containing compounds as described in U.S. Pat. No. 5,112,932 .
- an advanced epoxy-isocyanate copolymer such as those sold commercially as D.E.R.® 592 and D.E.R.® 6508 (Dow Chemical) can be used.
- the epoxy resin preferably is a bisphenol-type epoxy resin or mixture thereof with up to 10 percent by weight of another type of epoxy resin.
- the bisphenol type epoxy resin is a liquid epoxy resin or a mixture of a solid epoxy resin dispersed in a liquid epoxy resin.
- the most preferred epoxy resins are bisphenol-A based epoxy resins and bisphenol-F based epoxy resins.
- An especially preferred epoxy resin is a mixture of a diglycidyl ether of at least one polyhydric phenol, preferably bisphenol-A or bisphenol-F, having an epoxy equivalent weight of from 170 to 299, especially from 170 to 225, and at least one second diglycidyl ether of a polyhydric phenol, again preferably bisphenol-A or bisphenol-F, this one having an epoxy equivalent weight of at least 300, preferably from 310 to 600.
- the proportions of the two types of resins are preferably such that the mixture of the two resins has an average epoxy equivalent weight of from 225 to 400.
- the mixture optionally may also contain up to 20%, preferably up to 10%, of one or more other epoxy resin.
- the epoxy resin may include at least about 10 weight percent, based on the total weight of the epoxy adhesive composition, preferably at least about 15 weight percent, and most preferably at least about 20 weight percent, based on the total weight of the epoxy adhesive composition. In some embodiments, the epoxy resin preferably comprises up to about 70 weight percent of the epoxy adhesive composition, more preferably up to about 60 weight percent, and most preferably up to about 50 weight percent, based on the total weight of the epoxy adhesive composition.
- the amphipathic block copolymer comprises a carboxylic terminated ethylene oxide-butylene oxide block copolymer, i.e., a copolymer having at least one block segment that is miscible or partially miscible with the epoxy resin, and at least one block segment which is immiscible with epoxy resin.
- block segments which are miscible in epoxy resin include in particular polyethylene oxide, polypropylene oxide, poly(ethylene oxide-co-propylene oxide), and poly(ethylene oxide-ran-propylene oxide) blocks, and mixtures thereof.
- block segments immiscible in epoxy resin include in particular polyether blocks prepared from alkylene oxides which contain at least four C atoms, such as butylene oxide, hexylene oxide, and/or dodecylene oxide.
- block segments that are immiscible in epoxy resin also include in particular oxides of polyethylene, polyethylene-propylene, polybutadiene, polyisoprene, polydimethylsiloxane, and polyalkyl methacrylate blocks and mixtures thereof.
- amphiphilic block copolymers examples include those described in WO 2006/052725 A1 , WO 2006/052726 A1 , WO 2006/052727 A1 , WO 2006/052728 A1 , WO 2006/052729 A1 , WO 2006/052730 A1 , or WO 2005/097893 A1 .
- a particularly preferred class of amphiphilic block copolymers is available from The Dow Chemical Company under the product name FORTEGRATM.
- the amount of the amphiphilic block copolymer in the adhesive composition generally ranges from about 1 to 10 weight percent, based on the total weight of the adhesive composition, and in particular, from about 5 to 8, and more particularly, from about 6 to 7 weight percent, based on the total weight of the adhesive composition.
- the polyurethane based toughener comprises a polyurethane polymer that is a reaction product of a polyol and an aliphatic diisocyanate, such as 1,6 hexane diisocyanate and isophorone diisocyanate.
- polyurethane based tougheners in accordance with the present invention include end groups that are either reactive toward the epoxy curatives, or are removed so that the isocyanate groups are available to react with the epoxy curatives.
- diisocyanates that may be used in the preparation of the polyurethane polymer include aromatic diisocyantes, toluene diisocyanate (TDI) and methylene diphenyl diisocyanate, MDI, aliphatic and cycloaliphatic isocyanates , such as 1,6-hexamethylene diisocyanate (HDI), 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethyl-cyclohexane (isophorone diisocyanate, IPDI), and 4,4'-diisocyanato dicyclohexylmethane, (H 12 MDI or hydrogenated MDI).
- HDI 1,6-hexamethylene diisocyanate
- IPDI isophorone diisocyanate
- H 12 MDI or hydrogenated MDI 4,4'-diisocyanato dicyclohexylmethane
- the polyol component may comprise polyether polyols, which are made by the reaction of epoxides with an active hydrogen containing starter compounds, or polyester polyols, which are made by the polycondensation of multifunctional carboxylic acids and hydroxyl compounds.
- the isocyanate groups of the polyurethane-based toughener may be capped or blocked with an end group, such as a phenolic compound, an aminophenolic compound, carboxylic acid group, or hydroxyl group.
- Preferred capping groups include phenolic compounds, such as bisphenol-A, or diallyl bisphenol-A and diisopropylamine.
- the polyurethane toughener comprise a polyol component having good flexibility.
- polyol components having relatively high molecular weights may provide improved flexibility.
- the polyol may have a molecular weight ranging between 2,000 and 12,000 Daltons, and in particular, between 3,000 and 10,000.
- the polyol comprises a polyether chain having from 4 to 12 consecutive carbon atoms between each pair of ether groups, and preferably having from 4 to 8 consecutive carbon atoms between each pair of ether groups.
- the polyol component of the polyurethane based toughener may range from about 70 to 90 weight percent, based on the total weight of the polyurethane based toughener.
- the polyol component of the polyurethane based toughener is from about 72 to 88 weight percent, and more preferably, from about 75 to 85 weight percent, based on the total weight of the polyurethane based toughener.
- urethane based tougheners examples include a hydroxyl capped polyurethane available under the product name INT LMB 6333 FLEXIBILIZER, and available from The Dow Chemical Company, and a diisopropylamine capped urethane available under the product name RAM DIPA, which is also available from The Dow Chemical Company.
- the amount of the polyurethane based toughener generally ranges from about 10 to 25 weight percent, based on the total weight of the epoxy adhesive composition, and in particular, from about 10 to 20, and more particularly, from about 14 to 18 weight percent, based on the total weight of the epoxy adhesive composition.
- the adhesive may include up to about 25, up to about 20, up to about 18, up to about 16, or up to about 14 weight percent, of the polyurethane based toughener, based on the total weight of the epoxy adhesive composition.
- the epoxy adhesive composition further contains a curing agent.
- the curing agent is selected together with any catalysts such that the adhesive cures when heated to a temperature of 80° C, preferably at least 100° C or greater, but cures very slowly if at all at room temperature (about 22° C.) and at temperatures up to at least 50° C.
- Such suitable curing agents include boron trichloride/amine and boron trifluoride/amine complexes, dicyandiamide, melamine, diallylmelamine, guanamines such as acetoguanamine and benzoguanamine, aminotriazoles such as 3-amino-1,2,4-triazole, hydrazides such as adipic dihydrazide, stearic dihydrazide, isophthalic dihydrazide, semicarbazide, cyanoacetamide, and aromatic polyamines such as diaminodiphenylsulphones.
- dicyandiamide, isophthalic acid dihydrazide, adipic acid dihydrazide and 4,4'-diaminodiphenylsulphone is particularly preferred.
- the curing agent is used in sufficient amount to cure the composition.
- the curing agent suitably constitutes at least about 1.5 weight percent of the epoxy adhesive composition, and more preferably at least about 2.5 weight percent.
- the curing agent preferably constitutes up to about 15 weight percent of the epoxy adhesive composition, more preferably up to about 10 weight percent, and most preferably up to about 6 weight percent.
- the epoxy adhesive composition will in most cases contain a catalyst for the cure of the adhesive.
- a catalyst for the cure of the adhesive are ureas such as p-chlorophenyl-N,N-dimethylurea (Monuron), 3-phenyl-1,1-dimethylurea (Phenuron), 3,4-dichlorophenyl-N,N-dimethylurea (Diuron), N-(3-chloro-4-methylphenyl)-N',N'-dimethylurea (Chlortoluron), tert-acryl- or alkylene amines like benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, piperidine or derivates thereof, imidazole derivates, in general C.sub.1-C.sub.12 alkylene imidazole or N-arylimidazols, such as 2-ethyl-2-methyl-imidazol, or N-butylimida
- the catalyst may be encapsulated or otherwise be a latent type which becomes active only upon exposure to elevated temperatures.
- the catalyst is present in the epoxy adhesive composition in the amount of at least about 0.1 weight percent of the structural adhesive, and most preferably about 0.2 weight percent.
- the epoxy curing catalyst is present in an amount of up to about 2 weight percent of the structural adhesive, more preferably up to about 1.0 weight percent, and most preferably about 0.7 weight percent.
- Another optional component is a bisphenol compound that has two or more, preferably two, phenolic hydroxyl groups per molecule.
- suitable bisphenol compounds include, for example, resorcinol, catechol, hydroquinone, bisphenol, bisphenol A, bisphenol AP (1,1-bis(4-hydroxylphenyl)-1-phenyl ethane), bisphenol F, bisphenol K, tetramethylbiphenol and the like.
- the bisphenol component can be dissolved into the epoxy adhesive composition or present in the form of finely divided particles.
- the bisphenol component is pre-reacted with an epoxy resin (which may include a rubber-modified epoxy resin, if present) to advance the resin somewhat.
- the bisphenol component is preferably used in an amount from about 3 to about 35 parts by weight per 100 parts by weight of the rubber component. A preferred amount is from about 5 to about 25 parts by weight per 100 parts by weight of the rubber component.
- the bisphenol component When added directly into the structural adhesive, it usually constitutes from 0.25 to 2 weight percent, especially 0.4 to 1.5 weight percent, of the epoxy adhesive composition.
- the epoxy adhesive composition of the invention may contain various other optional components. Among these, fillers, rheology modifiers or pigments, one or more additional epoxy resins and a core-shell rubber are particularly preferred.
- a filler, rheology modifier and/or pigment is preferably present in the epoxy adhesive composition. These can perform several functions, such as (1) modifying the rheology of the epoxy adhesive composition in a desirable way, (2) reducing overall cost, (3) absorbing moisture or oils from the epoxy adhesive composition or from a substrate to which it is applied, and/or (4) promoting cohesive, rather than adhesive, failure.
- Examples of these materials include calcium carbonate, calcium oxide, talc, coal tar, carbon black, textile fibers, glass particles or fibers, aramid pulp, boron fibers, carbon fibers, mineral silicates, mica, powdered quartz, hydrated aluminum oxide, bentonite, wollastonite, kaolin, fumed silica, silica aerogel or metal powders such as aluminum powder or iron powder.
- calcium carbonate, talc, calcium oxide, fumed silica and wollastonite are preferred, either singly or in some combination, as these often promote the desired cohesive failure mode.
- the epoxy adhesive composition can further contain other additives such as diluents, plasticizers, extenders, pigments and dyes, fire-retarding agents, thixotropic agents, flow control agents, thickeners such as thermoplastic polyesters, gelling agents such as polyvinylbutyral, adhesion promoters and antioxidants.
- additives such as diluents, plasticizers, extenders, pigments and dyes, fire-retarding agents, thixotropic agents, flow control agents, thickeners such as thermoplastic polyesters, gelling agents such as polyvinylbutyral, adhesion promoters and antioxidants.
- Fillers, rheology modifiers, gelling agents, thickeners and pigments preferably are used in an aggregate amount of about 5 weight percent, based on the total weight of the adhesive composition or greater, more preferably about 10 weight percent of the epoxy adhesive composition or greater. In one embodiment, such components may preferably be present in an amount of up to about 25 weight percent of the epoxy adhesive composition, more preferably up to about 20 weight percent.
- the epoxy adhesive composition can be applied by any convenient technique. It can be applied cold or be applied warm if desired. It can be applied by extruding it from a robot into bead form on the substrate, it can be applied using manual application methods such as a caulking gun, or any other manual application means.
- the epoxy adhesive composition can also be applied using jet spraying methods such as a steaming method or a swirl technique.
- the swirl technique is applied using an apparatus well known to one skilled in the art such as pumps, control systems, dosing gun assemblies, remote dosing devices and application guns.
- the epoxy adhesive composition may be applied to the substrate using a streaming process. Generally, the epoxy adhesive composition is applied to one or both substrates. The substrates are contacted such that the epoxy adhesive composition is located between the substrates to be bonded together.
- the epoxy adhesive composition may be cured by heating to a temperature at which the curing agent initiates cure of the epoxy resin in the epoxy adhesive composition.
- this temperature is about 80° C or above, preferably 100° C or above.
- the temperature is about 220° C or less, and more preferably about 180° C or less.
- the epoxy adhesive composition of the invention can be used to bond a variety of substrates together including wood, metal, coated metal, aluminum, a variety of plastic and filled plastic substrates, fiberglass and the like.
- the adhesive is used to bond parts of automobiles together or parts to automobiles.
- Such parts can be steel, coated steel, galvanized steel, aluminum, coated aluminum, plastic and filled plastic substrates.
- the frame components are often metals such as cold rolled steel, galvanized metals, or aluminum.
- the components that are to be bonded to the frame components can also be metals as just described, or can be other metals, plastics, composite materials, and the like.
- Adhesion to brittle metals such as steel coated with galvaneal is of particular interest in the automotive industry. Galvaneal tends to have a zinc-iron surface that is somewhat rich in iron content and is brittle for that reason.
- a particular advantage of this invention is that the cured epoxy adhesive composition bonds well to metals with a brittle coating, such as galvaneal.
- Another application of particular interest is the bonding of aerospace components, particularly exterior metal components or other metal components that are exposed to ambient atmospheric conditions during flight.
- the epoxy adhesive composition once cured preferably has a Young's modulus of about 1000 MPa as measured according to DIN EN ISO 527-1. More preferably, the Young's modulus is about 1200 MPa or greater.
- the cured epoxy adhesive composition demonstrates a tensile strength of about 25 MPa or greater, more preferably about 30 MPa or greater, and most preferably about 35 MPa or greater.
- the lap shear strength of a 1.5 mm thick cured adhesive layer is about 15 MPa or greater, more preferably about 20 MPa or greater, and most preferably about 25 MPa or greater measured according to DIN EN 1465.
- embodiments of the present invention provide an epoxy adhesive composition having improved wash off resistance when subjected to an e-coat bath treatment.
- an epoxy functionalized amphiphilic block copolymer into the epoxy adhesive composition improves resistance to adhesive removal during the e-coat bath treatment.
- embodiments of the present invention exhibit an adhesive wash-off resistance of less than 20% when subjected to the e-coat bath treatment, and in particular, less than 18%, and more particularly, less than 15%, and even more particularly, less than 12% as measured as the percent difference between an epoxy formulation having a viscosity greater than 350 pascal second and the inventive formulation when subjected to the "indirect impingement spray" test.
- embodiments of the present invention having an epoxy functionalized amphiphilic block copolymer provide improvements in wash off resistance in comparison to similar or identical compositions that did not include the epoxy functionalized amphiphilic block copolymer.
- the indirect impingement spray test comprises depositing a bead of an epoxy formulation (8 mm x 125 mm) onto a panel.
- a stream of fluid e.g., water
- Movement of the bead is then measured at three locations and an average value is determined. This procedure is performed for the control and inventive formulations and the percent differences between the control and inventive formulations are determined.
- the epoxy functionalized amphiphilic block copolymer comprises a reaction product between a carboxylic terminated ethylene oxide-butylene oxide block copolymer and an epoxy resin, such as diglycidyl ethers of polyhydric phenol compounds.
- an epoxy resin such as diglycidyl ethers of polyhydric phenol compounds.
- examples of such epoxy resins include diglycidyl ethers of bisphenol A, such as are sold by Dow Chemical under the designations D.E.R.® 330, D.E.R.® 331, D.E.R. ® 332, D.E.R.® 383, D.E.R.® 661 and D.E.R.® 662 resins.
- the epoxy functionalized amphiphilic block copolymer is a reaction product between a carboxylic terminated ethylene oxide-butylene oxide block copolymer sold under the trademark FORTEGRA® 202, and an epoxy resin sold under the designation D.E.R.® 331, both of which are available from The Dow Chemical Company.
- the resulting epoxy adhesive composition has a viscosity less than 300 pascal second (300k centipoise), and more preferably, a viscosity ranging from 225 to 300 pascal second, such as from 245 to 280 pascal second, from 250 to 275 pascal second, and from 260 to 270 pascal second.
- the molecular weight of the epoxy functionalized amphiphilic block copolymer be from about 5,000 g/mole to 20,000 g/mole, and more preferably 8,000 g/mole to 16,000 g/mole.
- the amount of the epoxy functionalized amphiphilic block copolymer in the epoxy adhesive composition generally ranges from about 10 to 20 weight percent, based on the total weight of the epoxy adhesive composition, and in particular, from about 12 to 18, and more particularly, from about 12 to 16 weight percent, based on the total weight of the epoxy adhesive composition.
- suitable fillers may include calcium carbonate, calcium oxide, talc, coal tar, carbon black, textile fibers, glass particles, fibers, or spheres, aramid pulp, boron fibers, carbon fibers, mineral silicates, mica, powdered quartz, hydrated aluminum oxide, bentonite, wollastonite, kaolin, fumed silica, silica aerogel or metal powders such as aluminum powder or iron powder.
- hollow glass spheres are preferred, either singly or in some combination with other filler components.
- a one-component epoxy adhesive composition in accordance with the invention was prepared and evaluated in comparison to a comparative adhesive that did not include an epoxy functionalized amphiphilic block copolymer.
- Reference epoxy adhesive compositions and comparative examples were also prepared and subjected to an impact peel test and a T-Peel failure mode test to assess and evaluate their low temperature impact resistance.
- the resins and tougheners were added to the Speed mixing cup to which the liquid components were added. This was mixed for 1 minute at 2,200 rpm. The solids, except the catalyst, were then added and the composition was mixed for 3 minutes at 2,200 rpm. The sides of the mixing cup were scraped down and the composition was cooled to below 50° C. The catalyst was added to the Speed Mixing cup and speed mixed for 1 minute at 2,200 rpm. The composition was then added to a dual planetary Ross Mixer and mixed for 20 minutes at the slowest speed at a temperature of 40°C and under vacuum.
- T-Peel specimens were prepared and tested according to the ASTM Standard ASTM D1876.
- the substrate used was 0.8 mm thick GMC-5E cold rolled steel supplied by ACT Laboratories, Inc.
- Test coupons were cut into 1 inch x 4 inch strips and 1 inch of the 4 inch length was bent at a 90° angle.
- the 3 in 2 bonding overlap section of each coupon was cleaned with acetone.
- the adhesive was applied to the bonding section of the coupon and 10 mil glass bead spacers were applied on top to control the bond gap.
- Another coupon was laid on top and the specimen was assembled. The edges of the assembly were scraped clean using a spatula and held together with clips while curing for a 30 minute, 170°C bake cycle in a programmable Blue M Electric Oven programmed with repeatable heat up and cool down cycles.
- the average load per unit of bond width was measured using an Instron® 5500R Materials Testing System (Instron Corporation). Mechanical grips were used to hold the T-Peel samples in place. The distance between the grips was two inches. The crosshead speed was 50 mm/min. The computer measured the load as a function of crosshead displacement and loads were converted to Newtons of force per mm of bond width. After each T-Peel specimen was tested to failure, a failure mode was assigned by visual evaluation. Failure modes were classified as either Adhesive Failure or Cohesive Failure and given a number ranking with a number system with 100% Adhesive Failure being assigned a 1 and 100% Cohesive Failure being assigned a 5.
- Impact Peel specimens were prepared and tested according to the ISO Standard ISO 11343.
- the substrate used was 0.8 mm thick GMC-5E cold rolled steel supplied by ACT Laboratories, Inc.
- Test coupons were cut into 20 mm x 100 mm strips. 10 mil thick Teflon tape was applied to the end and middle of one coupon marking off the bonding area of 20 mm X 30 mm.
- the bonding section of each coupon was cleaned with Acetone.
- the adhesive was applied to the bonding section of the coupon and another coupon was laid on top to assemble the specimen.
- the edges of the assembly were scraped clean using a spatula and held together with clips while curing for a 30 minute 170°C bake cycle in a programmable Blue M Electric Oven programmed with repeatable heat up and cool down cycles. After curing, the bonded section of the assembly was marked and clamped in a vice. The free ends were bent by hand to allow the insertion of a wedge for impact testing.
- Impact testing was performed with an Instron Dynatup Crush Tower in accordance with ISO 11343 wedge impact method.
- the specimens were placed inverted on a fixed wedge.
- the crosshead with the load cell and 50 lb. weight attached was dropped from a fixed height at a velocity of 6.7 ft/s.
- the cleavage force was measured and converted to N/mm of bond line.
- Specimens tested at -40°C were condition for 1 hour in a freezer set to -43°C and then immediately tested at room temperature. This procedure reproducibly insures that the adhesive and coupon are at -40°C at the instant of impact.
- Table 2 Impact Peel, T-Peel, and failure mode Sample No. Impact Peel at room temperature (N/mm) Impact Peel at -40° C (N/mm) T-Peel (N/mm) Failure mode Reference Example 1 23.1 13.6 8.1 5 Comparative Example 2 20.7 5.7 7.7 3 Reference Example 2 38.7 32.9 --- -- Comparative Example 1 -- 27 -- -- Comparative Example 3 35 26 -- -- Comparative Example 4 -- 1 -- --
- Reference Example and Comparative Example 2 were formulated to compare the difference in impact peel and T-Peel by replacing an elastomer component with an amphipathic block copolymer. From this comparison, it can be seen that the amphipathic block copolymer provides improvement in both peel strength and T-Peel.
- Comparative Example 1 (not within the scope of the claims) was prepared and compared to Comparative Examples 1, 3, and 4.
- the formulation of Comparative Example 1 did not include an amphipathic block copolymer, but rather only included a polyurethane. From this comparison, it is evident that the composition comprising a combination of one or more epoxy resins, at least one polyurethane based toughener, and at least one amphipathic block copolymer provides improvements in impact peel strength over the formulations of the comparative examples.
- epoxy adhesives can be used to prepare composite structures having impact peel strengths of at least 13 N/mm at a temperature of -40° C, wherein the impact peel strength is measure in accordance with ISO 11343 wedge impact method, and preferably at least 15 N/mm, and more preferably, at least 20 N/mm.
- the T-peel test as with any adhesion test must exhibit the appropriate failure mode and strength.
- Original equipment auto manufacturers, OEMs demand that all test specimens exhibit cohesive failure, which is failure in the adhesive matrix. Interfacial failure (adhesive failure) is unacceptable.
- the T-peel test using cold rolled steel is one of the most difficult tests to attain cohesive failure, even more difficult than the impact peel test. For this reason, the automotive OEMs examine the failure mode for this test very closely.
- an epoxy composition having an epoxy functionalized amphiphilic block copolymer was prepared and evaluated in comparison to several comparative formulations that did not include the epoxy functionalized amphiphilic block copolymer.
- the inventive epoxy adhesive composition and comparative examples were subjected to an e-bath treatment and then evaluated to determine the amount of adhesive removed during the wash treatment.
- a control epoxy formulation was prepared that comprised an epoxy resin, a polyurethane based toughener, an elastomeric component, and filler components.
- the Control formulation was selected based on the formulation's high viscosity (e.g., greater than 350 pascal second) and resulting e-wash off resistance.
- Samples A-H were prepared that comprised an epoxy base formulation to which either an epoxy functionalized amphiphilic block copolymer (Inventive Examples A-D), or an amphiphilic block copolymer (Comparative Examples E-H, not within the scope of the claims) were added.
- the epoxy base formulation included an epoxy resin, a polyurethane based toughener, fillers, and an epoxy curing agents.
- the epoxy base formulation of Table 3 was used to prepare the 8 epoxy formulations (Examples A-H in Table 4 below).
- the epoxy formulations in Table 4 were prepared with a dual asymmetric centrifugal FlackTek SpeedMixer® DAC 400 FVZ by Hauschild Engineering using the following procedure.
- a first step the resin and rubber components were added to a speed mixing cup to which the liquid components were then added. The added components were then mixed with the speed mixer for 1 minute at 2,200 rpm.
- the solid components were added with the exception of the catalyst component, and then mixed for 3 minutes at 2,200 rpm.
- the sides of the mixing cup were scraped down and the mixture was cooled below 50° C.
- the catalyst was then added and speed mixed for 1 minute at 2,200 rpm.
- the resulting mixture was then mixed in a dual planetary Ross Mixer for 20 minutes at the slowest speed at 40°C and 25 in Hg vacuum to de-air.
- Viscosities of the formulations in Table 4 were evaluated according to a simple steady shear rate flow test with a TA Instruments AR2000EX Stress Controlled Rheometer. A 25 mm parallel plate geometry was used with an initial gap setting of 475 ⁇ m. Adhesive squeeze out was then removed and the gap was set to 450 ⁇ m to maintain a consistent sample volume. Sample testing temperature was maintained at 38° C using the Peltier temperature control plate capable of 0.01° C resolution. A Peak Hold Flow Test was run at a shear rate of 3 1/s for 4 minutes with sampling every 10 seconds. The viscosity was taken at 3 minutes where steady state was achieved.
- the formulations in Table 4 were then evaluated for e-bath wash off resistance.
- the wash off resistance was conducted with a Dow Automotive spray tank designed for adhesive wash off testing.
- a spray nozzle that provided a fan shaped spray pattern was used.
- the nozzle was 3.7 mm wide by 2.8 mm high.
- the water temperature was maintained at 50° C with a fluid pressure set at 275 kPa.
- An 8 mm by 125 mm adhesive bead was applied to a 10.2 cm by 30.5 cm hot dipped galvanized steel panel cleaned with Acetone.
- the bead was formed using a trowel heated to 50°C with an 8 mm diameter half circle cut into the trowel.
- the spray was aimed to hit 1 cm above the adhesive bead for "indirect impingement spray" and was timed at 20 seconds of spray for each test.
- the initial bead position was pre-marked allowing for measurement of the movement of the bead.
- the bead movement was measured in mm at three locations, 25 mm from the ends and in the middle, and an average value was taken.
- Three panels of each adhesive were run inter mixing the order.
- the width of the bead and other measurements taken after testing were measured with a micrometer after baking the panel in a forced air oven at 160° C for 15 minutes to cure the adhesive.
- the average bead movement distance was then compared to the control formulation and a percent difference was calculated to quantify the wash off resistance.
- the e-bath wash off resistance of the inventive formulations is determined as a percent difference in movement of a bead of cured adhesive in comparison to the movement of a similar sized bead of a control formulation having a viscosity greater than 350 pascal second when subjected to an indirect impingement spray of water as described above.
- Table 5 The results are summarized in Table 5 below.
- an object of the invention is to provide an epoxy adhesive formulation having a relatively low viscosity (less than 300 pascal second) while having a wash off resistance as measured by the percent difference in movement of a bead of the inventive composition, and a bead of similar size Control formulation when subjected to an indirect impingement spray.
- epoxy formulations in accordance with the present invention will exhibit a percent difference of less than 20%, and in particular, less than 15%.
- Inventive Examples A-D which included the epoxy functionalized amphipathic block copolymer had viscosities less than 350 pascal second, and a percent difference in wash off resistance of less than 20%.
- Inventive Examples A-D exhibited a viscosity ranging between 247 and 266 pascal second, and a percent difference between 1 and 13.
- Comparative Examples E-H which included an amphipathic block copolymer, but did not include an epoxy functionalized amphipathic block copolymer exhibited viscosities ranging between 242 and 326, and a percent difference in comparison to the control that is between 64 and 110%.
- the epoxy formulations that did not include an epoxy functionalized amphipathic block copolymer did not provide the improvements in wash off resistance.
Claims (14)
- Einkomponenten-Klebstoffzusammensetzung, die Folgendes umfasst:ein oder mehrere Epoxidharze;mindestens einen polyurethanbasierten Schlagfestmacher;mindestens ein epoxidfunktionalisiertes, amphiphatisches Block-Copolymer; undein oder mehrere Epoxidhärtungsmittel;wobei das epoxidfunktionalisierte, amphiphatische Block-Copolymer ein Reaktionsprodukt eines Ethylenoxid-Butylenoxid-Block-Copolymers mit einer Carboxylendgruppe und ein Epoxidharz umfasst.
- Klebstoff nach Anspruch 1, wobei das Epoxidharz mindestens einen Diglycidylether eines Bisphenols enthält.
- Klebstoff nach Anspruch 1, wobei die Menge an Epoxid etwa 30 bis 60 Gewichtsprozent beträgt, basierend auf dem Gesamtgewicht der Klebstoffzusammensetzung.
- Klebstoff nach Anspruch 1, wobei der polyurethanbasierte Schlagfestmacher aliphatische Diisocyanatgruppen enthält, welche mit einer oder mehreren Blockierungs- oder Endgruppen aus Bisphenol A oder Diisopropylamin versehen sind.
- Klebstoff nach Anspruch 1, wobei die Menge an Polyurethan etwa 10 bis 25 Gewichtsprozent beträgt, basierend auf dem Gesamtgewicht der Klebstoffzusammensetzung.
- Klebstoff nach Anspruch 1, wobei die Menge an amphiphilischem Block-Copolymer etwa 2 bis 14 Gewichtsprozent beträgt, basierend auf dem Gesamtgewicht der Klebstoffzusammensetzung.
- Klebstoff nach Anspruch 1, der ferner mindestens einen Füller umfasst.
- Klebstoff nach Anspruch 7, wobei der Füller aus der Gruppe gewählt ist, bestehend aus Mineralfüllern, Glaspartikeln und Quarzglas.
- Verbundstruktur, die ein erstes Substrat, ein zweites Substrat und eine gehärtete Klebstoffzusammensetzung nach Anspruch 1 umfasst, welche das erste und das zweite Substrat miteinander verbindet.
- Verbundstruktur nach Anspruch 9, wobei das erste und das zweite Substrat beide aus Metall bestehen oder eines des ersten und des zweiten Substrates aus Metall besteht und das andere Substrat aus Kunststoff besteht.
- Verbundstruktur nach Anspruch 9, wobei die Verbundstruktur eine Schlagschälfestigkeit von mindestens 15 N/mm bei einer Temperatur von 40° C aufweist, wobei die Schlagschälfestigkeit gemäß dem Keilschlagverfahren nach ISO 11343 gemessen wird.
- Verfahren, das das Auftragen des Klebstoffs nach Anspruch 1 auf Oberflächen von zwei Substraten, und Härten des Klebstoffs zum Bilden einer Klebebindung umfasst.
- Verfahren nach Anspruch 12, wobei die beiden Substrate Metall beinhalten oder mindestens eines der Substrate ein Kunststoffmaterial beinhaltet.
- Klebstoff nach Anspruch 1, wobei die Klebstoffzusammensetzung eine Viskosität von unter 300 Pascal-Sekunde aufweist, bestimmt wie beschrieben in der Beschreibung, durch Durchführung einer Durchflussprüfung bei 38 °C mit konstanter Scherrate, mit parallelen Platten von 25 mm an einem spannungskontrollierten Rheometer, und eine Verbesserung der Abwaschbeständigkeit im Vergleich mit einer ähnlichen Klebstoffzusammensetzung aufweist, welche kein epoxidfunktionalisiertes amphipathisches Block-Copolymer enthält.
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PCT/US2015/044955 WO2016108958A1 (en) | 2014-12-31 | 2015-08-13 | Crash durable epoxy adhesive compositions having improved low-temperature impact resistance and wash off resistance |
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WO2018081032A1 (en) | 2016-10-25 | 2018-05-03 | Dow Global Technologies Llc | Epoxy adhesive having improved low-temperature impact resistance |
EP3532527A1 (de) * | 2016-10-28 | 2019-09-04 | Dow Global Technologies, LLC | Aufprallbeständiger epoxidklebstoff mit verbesserter kälteschlagzähigkeit |
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EP3428045A1 (de) * | 2017-07-13 | 2019-01-16 | Sika Technology Ag | Einkomponentiger hitzehärtender epoxidklebstoff hoher auswaschbeständigkeit |
EP3697862B1 (de) * | 2017-10-18 | 2023-05-03 | DDP Specialty Electronic Materials US, Inc. | Klebstoffzusammensetzung |
WO2020102117A1 (en) * | 2018-11-13 | 2020-05-22 | Wynn Nathaniel C | Battery module with close-pitch cylindrical cells and method of assembly |
EP3973011A1 (de) * | 2019-05-21 | 2022-03-30 | DDP Specialty Electronic Materials US, LLC | Epoxidklebstoffzusammensetzung und verwendungsverfahren |
CN112592686B (zh) * | 2020-12-15 | 2022-12-13 | 固德电材系统(苏州)股份有限公司 | 一种风电叶片用高韧性粘合剂及其制备方法和应用 |
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- 2015-08-13 CN CN201580069173.1A patent/CN107001897A/zh active Pending
- 2015-08-13 US US15/509,877 patent/US10392539B2/en active Active
- 2015-08-13 EP EP15754083.2A patent/EP3240830B1/de active Active
- 2015-08-13 WO PCT/US2015/044955 patent/WO2016108958A1/en active Application Filing
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Publication number | Publication date |
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EP3240830A1 (de) | 2017-11-08 |
WO2016108958A1 (en) | 2016-07-07 |
US20170292049A1 (en) | 2017-10-12 |
CN107001897A (zh) | 2017-08-01 |
US10392539B2 (en) | 2019-08-27 |
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